CN113896531A - Low-loss composite microwave dielectric ceramic with stable temperature and preparation method thereof - Google Patents

Low-loss composite microwave dielectric ceramic with stable temperature and preparation method thereof Download PDF

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CN113896531A
CN113896531A CN202111323057.1A CN202111323057A CN113896531A CN 113896531 A CN113896531 A CN 113896531A CN 202111323057 A CN202111323057 A CN 202111323057A CN 113896531 A CN113896531 A CN 113896531A
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周媛媛
李健
刘福田
佟娜
刘茂云
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University of Jinan
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Abstract

The invention discloses a composite microwave dielectric ceramic material with high quality factor and stable frequency temperature coefficient and a preparation method thereof1/3Nb2/3)O3And forsterite Mg2SiO4The composition expression of the ceramic is (1-x) Ba (Mg)1/3Nb2/3)O3‑xMg2SiO4(x = 0.25-0.5). The invention overcomes Ba (Mg)1/ 3Nb2/3)O3Positive temperature coefficient of frequency and Mg of ceramics2SiO4The temperature coefficient of the negative frequency is larger, and the two-phase composite material keeps higher quality factor and can be used as a key material of various microwave components. The ceramic material adopts a solid phase sintering method, and the Nb is reduced by two-phase compounding2O5The amount of the use toolHas the characteristics of simple preparation and low cost.

Description

Low-loss composite microwave dielectric ceramic with stable temperature and preparation method thereof
Technical Field
The invention belongs to the technical field of electronic ceramics, and relates to a low-loss composite microwave dielectric ceramic with stable temperature and a preparation method thereof.
Background
As a key material for manufacturing microwave communication devices such as dielectric resonators and filters, a microwave dielectric ceramic should have an appropriate dielectric constant εrHigh Q x f (low dielectric loss) and near-zero temperature coefficient of resonance frequencyfSo as to ensure the high efficiency, the definition and the accuracy of information transmission. With the development of the civil microwave communication industry to the microwave high frequency band, the microwave dielectric ceramic is required to have excellent dielectric property under the high frequency, and the product is required to have low price.
Widely applied to tantalum-based composite perovskite Ba (B ') in high frequency range'1/3Ta2/3)O3(B ═ Zn, Mg, Co) ceramics have a high quality factor (Q at 10 GHz)>10000) And a smaller temperature coefficient of resonance frequency (tau)f<5 ppm/c), but its high production cost is difficult to meet the increasing demand of microwave devices for civil use. Under the background of the application, the niobium-based composite perovskite Ba (B ') with relatively low production cost'1/3Nb2/3)O3Are receiving increasing attention. Theoretical studies have shown that Ba (Mg) with the same degree of order is present when different cations occupy the B' position1/3Nb2/3)O3The theoretical Q value of the dielectric material is the highest, and the dielectric material is the most promising next-generation microwave dielectric material for high-frequency application to replace tantalate composite perovskite. The microwave dielectric property of the BMN ceramic prepared by the traditional solid phase reaction method is as follows: epsilonr＝32，Q×f＝56 000GHz，τfWhen the measured value is +33 ppm/DEG C, the quality factor Qxf is not high enough, and the frequency temperature coefficient tau is not high enoughfIs too large to meet the requirements of practical application. For Ba (Mg)1/3Nb2/3)O3One method of modifying is to use a material with a negative temperature coefficient with Ba (Mg)1/3Nb2/3)O3The dielectric properties of the material are required to be not deteriorated by the chemical reaction generated during firing at high temperatures, so that the multiphase composite material is formed.
Forsterite Mg2SiO4Having a low dielectric constant (. epsilon.)r6-7) and high Q multiplied by f value (up to 240000 GHz), is a microwave dielectric material which is relatively suitable for being used as a low dielectric constant dielectric resonator, thereby being applied in microwave high frequency band, but the negative frequency temperature coefficient (tau) of the microwave dielectric materialf60-70 ppm/DEG C) is serious and cannot meet the requirements of practical application. Mg (magnesium)2SiO4Can be mixed with (Ca, Sr) TiO with perovskite structure3Coexisting at high temperature without chemical reaction, therefore, Mg2SiO4Expected to react with Ba (Mg)1/3Nb2/3)O3Mutually compensate the material with temperature coefficient, thereby obtaining the microwave dielectric material with excellent performance and low price.
Disclosure of Invention
The problems to be solved by the invention are as follows.
The invention provides a low-loss composite microwave dielectric ceramic with stable temperature and a preparation method thereof, which are used for solving the problem of Ba (Mg) in the prior art1/3Nb2/3)O3、Mg2SiO4Temperature coefficient of frequency τfSerious big problem, further improves the niobium-based composite perovskite Ba (Mg)1/3Nb2/3)O3The quality factor of the ceramic can be used as a next-generation high-frequency application type microwave dielectric material for replacing tantalate composite perovskite, the requirements of the current urgent development on low-loss microwave dielectric ceramic with simple process and low raw material cost and stable frequency and temperature are met, and the application requirements of the microwave communication industry are further met.
In order to achieve the purpose, the temperature-stable low-loss composite microwave dielectric ceramic is formed by compounding composite perovskite ceramic and forsterite, the composite perovskite ceramic and the forsterite do not generate chemical reaction when being sintered at high temperature, the temperature coefficients are complementary, and the composition expression is (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4(x＝0.25～0.5)。
The dielectric constant epsilon of the ceramic materialr16.42 to 23.62, high Q multiplied by f is 89400 GHz to 111000 GHz, and temperature coefficient of resonance frequency is tauf＝-2.8～9ppm/℃。
The preparation method of the temperature-stable low-loss composite microwave dielectric ceramic comprises the following steps.
(1) Preparation of Mg2SiO4A ceramic powder;
according to Mg2SiO4The stoichiometric ratio of MgO to SiO2Putting the mixture into a nylon ball milling tank, taking zirconia balls as grinding balls and absolute ethyl alcohol as a ball milling medium, fully mixing and ball milling, drying at 75-85 ℃, sieving and calcining to prepare Mg2SiO4A ceramic powder.
(2) Preparation of Ba (Mg)1/3Nb2/3)O3A ceramic powder;
according to Ba (Mg)1/3Nb2/3)O3In a stoichiometric ratio of BaCO3、MgO、Nb2O5Putting the mixture into a nylon ball milling tank, taking zirconia balls and absolute ethyl alcohol as ball milling media, fully mixing and ball milling, drying at 75-85 ℃, sieving and calcining to prepare Ba (Mg)1/3Nb2/3)O3A ceramic powder.
(3) Preparation of (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Composite microwave dielectric ceramic.
According to (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4In the design ratio of (1), weighing Mg in the step (1) and the step (2), wherein x is 0.25-0.52SiO4、Ba(Mg1/3Nb2/3)O3Ceramic powder is fully mixed and ball-milled, dried at 75-85 ℃, sieved, granulated, pressed into blocks and sintered at a certain temperature.
The specific process of ball milling in the step (1-3) is as follows: according to the reference: anhydrous ethanol: 1: 2: 2 for 4 hours in a ball milling mode, wherein the ball milling rotating speed is 250 r/min;
the calcination temperature in the step (1) is 1200-1300 ℃, and the heat preservation time is 4 hours;
the calcination temperature in the step (2) is 1150-1250 ℃, and the heat preservation time is 4 hours;
and (4) the sintering temperature in the step (3) is 1400-1460 ℃, and the temperature is kept for 4 hours and then the product is cooled.
The present invention has the following advantageous results.
The invention mainly uses the composite perovskite Ba (Mg) with positive resonant frequency temperature coefficient in the preparation of the low-loss composite microwave dielectric ceramic material with stable temperature1/3Nb2/3)O3The forsterite Mg with different structures, high Q value and negative resonant frequency temperature coefficient is introduced as a main phase2SiO4The coexistence of the two phases enables the temperature coefficients of the resonant frequency to compensate each other to achieve the effect of being close to zero, and simultaneously keeps moderate dielectric constant and higher quality factor; introduction of Mg2SiO4Reduce Ba (Mg)1/3Nb2/3)O3Sintering temperature of ceramics: (>At 1550 ℃), sintering the microwave dielectric ceramic material with compactness and excellent performance within the temperature range of 1400-1460 ℃; mg (magnesium)2SiO4The raw materials of (A) are sufficient at home, the price is low, and Ba (Mg)1/3Nb2/3)O3After compounding, reduce Nb2O5The usage amount is reduced, the preparation cost is reduced, and the method can be used for manufacturing 5G key microwave components such as a 5G dielectric filter, a radio frequency multilayer ceramic capacitor, a chip type microwave ceramic dielectric resonator, a microwave substrate and the like.
Drawings
Fig. 1 is an XRD pattern of the microwave dielectric ceramic material prepared in example 2 and example 4.
FIG. 2 is an SEM picture and an EDS energy spectrum of the microwave dielectric ceramic material prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The temperature-stable low-loss composite microwave dielectric ceramic material is formed by compounding a forsterite phase and a composite perovskite phase, and the composition expression of the ceramic material is (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Wherein x is 0.25.
The preparation method of the temperature-stable low-loss composite microwave dielectric ceramic material comprises the following steps.
(1) Preparation of Mg2SiO4A ceramic powder;
according to Mg2SiO4The stoichiometric ratio of MgO and SiO is weighed2Then ball-milling for 4h, drying, sieving, calcining at 1300 deg.C for 4h to obtain Mg2SiO4A ceramic powder.
(2) Preparation of Ba (Mg)1/3Nb2/3)O3A ceramic powder;
according to Ba (Mg)1/3Nb2/3)O3In a stoichiometric ratio of (A), weighing BaCO3MgO and Nb2O5Then ball milling for 4h, drying, sieving, calcining at 1200 deg.C for 4h to obtain Ba (Mg)1/3Nb2/3)O3A ceramic powder.
(3) Preparation of (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Composite microwave dielectric ceramic.
At 0.75Ba (Mg)1/3Nb2/3)O3-0.25Mg2SiO4The design proportion of (1) and (2) is weighed2SiO4And Ba (Mg)1/3Nb2/3)O3And performing ball milling for 4 hours, drying, sieving, granulating, pressing and forming, and performing heat preservation sintering at 1400-1460 ℃ for 4 hours to obtain the low-loss composite microwave dielectric ceramic material with stable temperature.
The properties of the group of ceramic materials reach the following indexes.
Sintering the mixture in air at 1400-1460 ℃ to form ceramic, and measuring the dielectric constant epsilon under the microwave frequency bandr23.62(8.98GHz), quality factor Q × f 102000 GHz, and temperature coefficient of resonance frequency τf＝9ppm/℃。
Example 2
The temperature-stable low-loss composite microwave dielectric ceramic material is formed by compounding a forsterite phase and a composite perovskite phase, and the composition expression of the ceramic material is (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Wherein x is 0.3.
The preparation method of the temperature-stable low-loss composite microwave dielectric ceramic material comprises the following steps.
(1) Preparation of Mg2SiO4A ceramic powder;
according to Mg2SiO4The stoichiometric ratio of MgO and SiO is weighed2Then ball-milling for 4h, drying, sieving, calcining at 1300 deg.C for 4h to obtain Mg2SiO4A ceramic powder.
(2) Preparation of Ba (Mg)1/3Nb2/3)O3A ceramic powder;
according to Ba (Mg)1/3Nb2/3)O3In a stoichiometric ratio of (A), weighing BaCO3MgO and Nb2O5Then ball milling for 4h, drying, sieving, calcining at 1200 deg.C for 4h to obtain Ba (Mg)1/3Nb2/3)O3A ceramic powder.
(3) Preparation of (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Composite microwave dielectric ceramic.
At 0.7Ba (Mg)1/3Nb2/3)O3-0.3Mg2SiO4The design proportion of (1) and (2) is weighed2SiO4And Ba (Mg)1/3Nb2/3)O3And performing ball milling for 4 hours, drying, sieving, granulating, pressing and forming, and performing heat preservation sintering at 1400-1460 ℃ for 4 hours to obtain the low-loss composite microwave dielectric ceramic material with stable temperature.
The properties of the group of ceramic materials reach the following indexes.
Sintering the mixture in air at 1400-1460 ℃ to form ceramic, and measuring the dielectric constant epsilon under the microwave frequency bandr21.87(9.30GHz), Q × f 111000 GHz, and temperature coefficient of resonance frequency τf＝6.1ppm/℃。
Example 3
The temperature-stable low-loss composite microwave dielectric ceramic material is formed by compounding a forsterite phase and a composite perovskite phase, and the composition expression of the ceramic material is (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Wherein x is 0.35.
The preparation method of the temperature-stable low-loss composite microwave dielectric ceramic material comprises the following steps.
(1) Preparation of Mg2SiO4A ceramic powder;
according to Mg2SiO4The stoichiometric ratio of MgO and SiO is weighed2Then ball-milling for 4h, drying, sieving, calcining at 1300 deg.C for 4h to obtain Mg2SiO4A ceramic powder.
(2) Preparation of Ba (Mg)1/3Nb2/3)O3A ceramic powder;
according to Ba (Mg)1/3Nb2/3)O3In a stoichiometric ratio of (A), weighing BaCO3MgO and Nb2O5Then ball milling for 4h, drying, sieving, calcining at 1200 deg.C for 4h to obtain Ba (Mg)1/3Nb2/3)O3A ceramic powder.
(3) Preparation of (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Composite microwave dielectric ceramic.
At 0.65Ba (Mg)1/3Nb2/3)O3-0.35Mg2SiO4The design proportion of (1) and (2) is weighed2SiO4And Ba (Mg)1/3Nb2/3)O3And performing ball milling for 4 hours, drying, sieving, granulating, pressing and forming, and performing heat preservation sintering at 1400-1460 ℃ for 4 hours to obtain the low-loss composite microwave dielectric ceramic material with stable temperature.
The properties of the group of ceramic materials reach the following indexes.
Sintering the mixture in air at 1400-1460 ℃ to form ceramic, and measuring the dielectric constant epsilon under the microwave frequency bandr20.59(9.560GHz), quality factor Qxf 99400 GHz, temperature coefficient of resonance frequency tauf＝4.6ppm/℃。
Example 4
The temperature-stable low-loss composite microwave dielectric ceramic material is formed by compounding a forsterite phase and a composite perovskite phase, and the ceramic materialThe composition expression of the porcelain material is (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Wherein x is 0.4.
The preparation method of the temperature-stable low-loss composite microwave dielectric ceramic material comprises the following steps.
(1) Preparation of Mg2SiO4A ceramic powder;
according to Mg2SiO4The stoichiometric ratio of MgO and SiO is weighed2Then ball-milling for 4h, drying, sieving, calcining at 1300 deg.C for 4h to obtain Mg2SiO4A ceramic powder.
(2) Preparation of Ba (Mg)1/3Nb2/3)O3A ceramic powder;
according to Ba (Mg)1/3Nb2/3)O3In a stoichiometric ratio of (A), weighing BaCO3MgO and Nb2O5Then ball milling for 4h, drying, sieving, calcining at 1200 deg.C for 4h to obtain Ba (Mg)1/3Nb2/3)O3A ceramic powder.
(3) Preparation of (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Composite microwave dielectric ceramic
At 0.6Ba (Mg)1/3Nb2/3)O3-0.4Mg2SiO4The design proportion of (1) and (2) is weighed2SiO4And Ba (Mg)1/3Nb2/3)O3And performing ball milling for 4 hours, drying, sieving, granulating, pressing and forming, and performing heat preservation sintering at 1400-1460 ℃ for 4 hours to obtain the low-loss composite microwave dielectric ceramic material with stable temperature.
The properties of the group of ceramic materials reach the following indexes.
Sintering the mixture in air at 1400-1460 ℃ to form ceramic, and measuring the dielectric constant epsilon under the microwave frequency bandr18.92(9.90GHz), quality factor Q × f 91200 GHz, and temperature coefficient of resonance frequency τf＝2.6ppm/℃。
Example 5
The temperature-stabilized low loss of the present inventionThe composite microwave dielectric ceramic material is formed by compounding a forsterite phase and a composite perovskite phase, and the composition expression of the ceramic material is (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Wherein x is 0.5.
The preparation method of the temperature-stable low-loss composite microwave dielectric ceramic material comprises the following steps.
(1) Preparation of Mg2SiO4A ceramic powder;
according to Mg2SiO4The stoichiometric ratio of MgO and SiO is weighed2Then ball-milling for 4h, drying, sieving, calcining at 1300 deg.C for 4h to obtain Mg2SiO4A ceramic powder.
(2) Preparation of Ba (Mg)1/3Nb2/3)O3A ceramic powder;
according to Ba (Mg)1/3Nb2/3)O3In a stoichiometric ratio of (A), weighing BaCO3MgO and Nb2O5Then ball milling for 4h, drying, sieving, calcining at 1200 deg.C for 4h to obtain Ba (Mg)1/3Nb2/3)O3A ceramic powder.
(3) Preparation of (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Composite microwave dielectric ceramic.
At 0.5Ba (Mg)1/3Nb2/3)O3-0.5Mg2SiO4The design proportion of (1) and (2) is weighed2SiO4And Ba (Mg)1/3Nb2/3)O3And performing ball milling for 4 hours, drying, sieving, granulating, pressing and forming, and performing heat preservation sintering at 1400-1460 ℃ for 4 hours to obtain the low-loss composite microwave dielectric ceramic material with stable temperature.
The properties of the group of ceramic materials reach the following indexes.
Sintering the mixture in air at 1400-1460 ℃ to form ceramic, and measuring the dielectric constant epsilon under the microwave frequency bandr16.42(10.750GHz), quality factor Qxf 89400 GHz, temperature coefficient of resonance frequency tauf＝-2.8ppm/℃。
The invention obtains the low-loss composite microwave dielectric ceramic material with stable temperature by a simple and effective solid-phase reaction sintering method. As can be seen from FIGS. 1 and 2, the phase composition of the ceramic material is Ba (Mg)1/3Nb2/3)O3And Mg2SiO4And no other impurity phase. With Mg2SiO4The phase contents were varied to correspond to the relative dielectric constants ε of the composite ceramic samples of examples 1 to 5, respectivelyrThe temperature coefficient of resonance frequency is between 16.42 and 23.62fThe dielectric ceramic material is between-2.8 and 9 ppm/DEG C, can keep a high quality factor Qxf between 89400 and 111000 GHz, has a sintering temperature between 1400 and 1460 ℃, and can meet the development requirements of high frequency and low cost of a 5G ceramic dielectric filter and a resonator.

Claims (7)

1. The temperature-stable low-loss composite microwave dielectric ceramic is characterized in that the ceramic material is formed by compounding a forsterite phase and a composite perovskite phase, and the chemical formula of the ceramic material is (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4(x＝0.25～0.5)。
2. The temperature-stable, low-loss composite microwave dielectric ceramic according to claim 1, further characterized in that the microwave dielectric ceramic has a dielectric constant εr16.42 to 23.62, high Q multiplied by f is 89400 to 111000 GHz, and temperature coefficient of resonance frequency is tauf＝-2.8～9ppm/℃。
3. (1-x) Ba (Mg) of claim 11/3Nb2/3)O3-xMg2SiO4A preparation method of the temperature-stable low-loss composite microwave dielectric ceramic is characterized by comprising the following steps:
(1) preparation of Mg2SiO4Ceramic powder
According to Mg2SiO4The stoichiometric ratio of MgO to SiO2Loading into a nylon ball milling tank, fully mixing and ball milling by taking zirconia balls as grinding balls and absolute ethyl alcohol as a ball milling medium, and drying at 75-85 DEG CThen sieving and calcining to prepare Mg2SiO4A ceramic powder.
(2) Preparation of Ba (Mg)1/3Nb2/3)O3Ceramic powder
According to Ba (Mg)1/3Nb2/3)O3In a stoichiometric ratio of BaCO3、MgO、Nb2O5Putting the mixture into a nylon ball milling tank, taking zirconia balls and absolute ethyl alcohol as ball milling media, fully mixing and ball milling, drying at 75-85 ℃, sieving and calcining to prepare Ba (Mg)1/ 3Nb2/3)O3A ceramic powder.
(3) Preparation of (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4Composite microwave dielectric ceramic
According to (1-x) Ba (Mg)1/3Nb2/3)O3-xMg2SiO4In the design ratio of (1), weighing Mg in the step (1) and the step (2), wherein x is 0.25-0.52SiO4、Ba(Mg1/3Nb2/3)O3Ceramic powder is fully mixed and ball-milled, dried at 75-85 ℃, sieved, granulated, pressed into blocks and sintered at a certain temperature.
4. The preparation method of the temperature-stable low-loss composite microwave dielectric ceramic according to claim 3, wherein the ball milling in the step (1-3) comprises the following specific processes: according to the reference: anhydrous ethanol: 1: 2: 2 for 4 hours, and the rotating speed of the ball mill is 250 r/min.
5. The method for preparing the temperature-stable low-loss composite microwave dielectric ceramic according to claim 3, wherein the calcination temperature in step (1) is 1200-1300 ℃ and the holding time is 4 hours.
6. The method for preparing the temperature-stable low-loss composite microwave dielectric ceramic according to claim 3, wherein the calcination temperature in the step (2) is 1150-1250 ℃ and the holding time is 4 hours.
7. The method for preparing the temperature-stable low-loss composite microwave dielectric ceramic according to claim 3, wherein the sintering temperature in the step (3) is 1400-1460 ℃, and the ceramic is cooled after being kept for 4 hours.
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